Oxidation of olefins



Nov. 2, 1954 R. B. EGBERT OXIDATION OF OLEFINS Filed Dec.

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N. oxoNm United States Patent() oxIDArioN oF oLEFlNs Robert B. Egbert, Roslyn Heights, N. Y., assignor to Chempatents, Inc., New York, N. Y., a corporation of Delaware Application December 28, 1950, Serial No. 203,119

11 Claims. (Cl. 260--348.5)

The present invention relates to the manufacture of olen oxides by direct oxidation in the presence of catalysts, and has particular reference to an improved procedure for increasing the overall yield of olen oxide, increasing the emciency of the system.

Oleiin oxides such as ethylene oxide are formed by passing a gaseous reaction mixture of ethylene and a source of oxygen such as air, through a reactor containingsilver catalyst. Inert gases such as nitrogen normally form a part of the reaction mixture, in order to stabilize the system against excessiveA conditions of reaction such as heat. The ethylene oxide end product is recovered from the reaction mixture, which isrecycled with proper adjustment of the proportion of ethylene and oxygen y constituents. A portion of the gaseous reaction mixture corresponding in volume to the volume of the new components added, is purged from the system. This purge results in loss of unconverted ethylene which seriously lowers the efficiency of the process.

In application Serial No. 159,839, filed May 3, 1950, it is proposed to carry out the oxidation reaction employing commercial gases containing'ethylene in dilute concentration as the starting material. The olen component of the gaseous reaction stream is selectivelyoxidized at a temperature of 240 C.-320 C. under a pressure of from 8 to 20 atmospheres. Hydrogen and unsaturated hydrocarbons other than olefins are preoxidized, and may remain in the reaction stream as inert gases. y

In copending application Serial No. 160,913, tiled May 9, 1950, it is proposed further that the olen content of the commercial gases be solvent extracted, and the relatively pure olefin mixed with oxygen and inert gases to form the reaction mixture.

It is an object of the present invention to effect further economies in the aforementioned processes for the oxidation of oleiins as well as commercial processes currently in use, increasing the overall yield in terms of olefin oxide.

AA further object is to improve processes for the manufacture of olefin oxides wherein commercial gases containing olefins in relatively dilute concentration are employed as starting materials;

A further object is to provide a novel procedure for use in connection with processes for the manufacture of ethylene oxide, wherein a portion of the gaseous reaction mixture is recycled through the system under controlled conditions of reaction whereby loss of ethylene from purging is minimized.

A further object is to provide an improved process for the manufacture of ethylene oxide wherein maximum selectivity is attained at an economical conversion level, resulting in the highest attainable efficiency at the lowest working and capital cost.

Other objects and advantages of the invention will be apparent from the following detailed description thereof taken in connection with the attached flow diagram wherein Figures 1 and 2 set forth diagrammatically, s ystems embodying the present invention, and the specific examples set forth hereinafter by way of description and amplification of the advantages of the invention.

In its broadest application, the invention comprehends the formation of a gaseous reaction mixture of olefin and a source of oxygen, for example, ethylene-and air, for the direct oxidation of the ethylene component in the presence of a silver catalyst, at temperatures of from 220 C.-350 C. and with pressures from 0 25 atmospheres gauge. The system employed is similar to that disclosed in application. Serial No. 159,839, wherein the gaseous reaction mixture is passed through a reactor and ethylene oxide formed scrubbed from the gaseous stream. The cleansed stream is recycled in the system, with the addition of ethylene and air to fortify the reactant proportions for further processing. A portion of the cleansed recycle gases must be purged from the system to compensate for the added reactants, and the purge gas will contain unconverted ethylene, which normally is lost to the process.

In commercial operations using this basic process, as high as 20% of the feed ethylene may be lost in the purge gases. This loss seriously deteriorates the operating eiciency of the` process. It is suggested that the purge gases be subjected to a secondary processing, to oxidize residual ethylene in the purge gases, thereby at least partially eliminating the loss of ethylene to the process.

It has now been discovered that by proper adjustment of the selectivity ratio of the primary ethylene oxidation reaction, with the conversion per pass ratio, this serious defect in operational efliciency is eliminated. The reaction stream in the primary oxidation reaction is maintained under reaction conditions attaining high selectivity but with low single pass yields. In combination with this step, the purge gases are subjected to a secondary ethylene oxidation reaction under conditions attaining a maximum yield of ethylene oxide for a single pass operation.

The term selectivity as used herein designates the ratio ethylene oxide formed ethylene reacted By maximum selectivity, it is meant that of the ethylene reacted, approximately 70% or more of ethylene oxide is formed. The term conversion as used herein designates the ratio ethylene reacted ethylene fed The term yield as used herein designates the ratio ethylene oxide ethylene fed Under the preferred method of operation, maximum selectivity is attained using a reaction stream containing 5% ethylene by volume. To attain maximum selectivity, the conversion per pass should not exceed appreciably 30 to 40%. It will be apparent that vthe gaseous reaction mixture, reacted under conditions set forth hereinafter to attain these optimum results, will containr considerable unreacted ethylene in the recycle gas, an appreciable portion of which normally is 10st in the purge gas.

In accordance with the invention, with recycle gases subjected to the aforesaid conditions of reaction in the primary reactor, the purge gases drawn off from the recycle gases are subjected to a secondary oxidation reaction, whereby residual ethylene in the purge gases is converted to ethylene oxide and recovered as valuable end product. As shown diagrammatically in Figure 1 of the flow diagram, the secondary oxidation reaction is characterized by maintenance of an optimum conversion ratio for a single pass operation, whereby some 42% of the ethylene otherwise lost to waste is recovered. The ethylene oxide is recovered from the purge gas in a water scrubbing operation, for recovery in the usual manner.

As an alternative procedure, the purge gas may be recycled after it has been passed over the catalyst in the secondary reactor, to reduce the ethylene concentration in the gases initially entering the secondary reactor. The

purge gas is cycled to the point of introduction of the gaseous reaction mixture into the secondary reactor, being mixed with an oxygen bearing gas in suitable proportion for the oxidation step. In both procedures, the nal purge gas may be vented to atmosphere.

A third alternative procedure is set forth diagrammatically in Figure 2 of the drawings, wherein the initial feed gas is pased through the primary reactor operated on the recycle basis as prescribed above, for maximum selectivity at an economic conversion level. The purge gases withdrawn to bleed inert gases from the system are passed through two or more secondary reactors in series, after admixture of additional air, under conditions of maximum single pass yield or conversion, the ethylene oxide' end product being recovered in each instance by a product sets in, whereby the overall yield per passdrop`s;'^

Vl/ith the "temperature of reaction constant; ia. moderate degree of control vover thereactioncan Vbe attained by changing'the rate ofilowof -thefe'ed gas over'the cata#T lyst.`.'1'

-For example, an increase of the ow rate from 300 cubic feet'perhourper 'reaction tub'e` to 600 vcubic feet per hour,'a relatively highilow rate; will decrease the c onVer'-` sion ratio. 4 ample, '245 Cgiand a ow rate of-3.00'to` 600 cubic feet per' hour," a" relatively low conversion ratio andhigh selectivityl will result? As the 'reaction temperature is raised, for example'to'290 C., theconver'sion is increased.-

.Thus, using va gasStream-containing 5% ethylene by volume at a flow rate 'of' 600 -cubic feet per hour at a temperature of'265 Ci., a conversion o`f A23.9% and a s'e lectivity of72.1% was attained. By slowingdown the rateof ,ow to' 300 cubic feet. per hour at a temperature o.-'265f 1C., 'a conversion of 41.2% with a selectivity of 62".8%`was'attained.

With a temperature of from 270 C. to 280 C., with a time of contact' with the catalyst in the order of three and one half seconds;' usin'gfa'5%i ethylene stream as in the primary. reactor, .a conversionmatior of 3,0% was at-y tained withk a selectivity off/% .4 On theotherhand, with a .temperature rangef of from 27.51C1.-2V85" .C. with atime of contact with the catalyst inthe order of .from.=fye\to six seconds, using a 3,1/2 (7a, ethylene stream as in the secondary reactor, a conversion'rperpass of 70% was attained, and a selectivityfofl5'2 ln orderv tov more clearly. explain the marked advantages attained by theprocess of. the invention, specic examples of ethylene oxidation reactions carried out in accordance with the principlesof the'invention are set forth hereinafter. ,l

E Jample'A A gaseous reaction mixture or feed gas of air, ethylene and recycle gas.5 was f fed` :to a :primary reactor containing 20.2feet-2y of 'silver catalyst, atea: temperature of 270? C.; with=approximately 3215A 'seconds tim-efof` contact with the catalyst.' The gaseousr'eaction mixturewas comprised 'as follows'- v; ,-wf: 1.. g: 1

Per cent Ethylene Oxygen-v nm Carbon dioxidev- Nitrogen l 100;() After reaction, the reaction mixture contained on adr'y4 basis:

, Per cent Ethylene 3.5 l Oxygen 4.j1 Carbony dioxide- 8.5 Ethylene oxide 1L05 Nitrogen f 8,2.8

The selectivity"wasl70%t, theconversion 30%, and the "For every 100 mols of -feed gas, about 10.5 mols must be purged'fromthe system,'"'fo'r purposes ofthe 'recycling step: In this"instance, the purge-gas contained 3.5%- ethylene. Approximately 1.3Vmol's"of"air were addedk to' raise'theioxygen` concentration in'the purge vgas to'6.0%

The; purge gasjthus modified had -ja composition:

With a relatively low temperature, for ex` The purge gas was then passed through a secondary reactor containing 40 feet ofi silver catalyst with a contact time of between one and two seconds. The resulting gas had the following conposition, on a dry basis:

Per cent Ethylene Oxygen 2.2 Carbon dioxide 9.7

The selectivity was 55%, the conversion 76%, and the yield 42% 'Tletotal 'end product, ethylene oxide, obtained from the primary and secondary reactors, was 1..203mols;l.05 molsfbeing obtained-'from the-prima`ry reactor.- MFl`1he totabethylene.consumed wast f' v "lloy make oxide 1.203l To make CO2 in primary reactor- 0145'- To make COzin vsecondary reactor 0.125 LOS'III 'fll'laflkplll'ge. ;;`;'.l........;;. Total The industrial eiciency wouldhave been 56%. Accordinglyg= lthe useof 4the secondary reactor' resultedin an-increase-in -findustrial eiciency of' 8.5%,t which wouldyamountto lan -increase in overall productionof (M3-lb. ofi ethylene xidepe'pound-ofethylene fed;

A feed gas of air, ethylene andrecycle gas, as in Example Aywere passed through the primar'y reactor,l 11.8, molsjoipurge"gasmaving ajcomposi'tionzl" Per cent Ethylene 3.1 Oxygen t 6.0 Carbn dioxide 7.6 lsllitrbgen" ';m ..l 83.3'

were passed through a tirst purge gas reactor, which was dplerat'ed'toobtain a'yild oiiab'fout;A 307%,"'The composltron of thxevpurge gas at the "outlet 'of' the first purge Per cen Ethylene 1.8 (D xfg'e'nv 4.2 Carb'ondioxide 8.5 Ethylene oxide 0.9 Ninko'genf 1 ^;-;f 84.6

The selectivity was 67%, the conversion 43% and the Ethylene 'Ihis mixture was then passed througha second purge gasfreactgr'having4 20 feet. of catalyst `Yin it. The comT positin'of the 'nal purge g'as'at 'th'eHotlet of lthe second PBI-g? g@ maag; was.:

, Per cent Ethylene 0.25 Oxygen 3.8 Carbon dioxide 8.9 Ethylene oxide 0.75 Nitrogen 86.3

The selectivity was 55%, the conversion 85% and the yield 47%. The ethylene consumption was as in Example A. The overall production of ethylene oxide was:

Mols

In primary reactor 1.05 In first purge reactor .106 In second purge reactor .097

Total 1.253

As before, the ethylene consumption was 1.87 mols Hence, the overall industrial eiciency of the process was 67%, as compared to 64.5% for the case where one purge reactor was used, and 56% where no purge reactor was used, an overall net increase of ll percentage points. The overall yield of ethylene oxide per pound of ethylene consumed increased by 0.17 pound. It is evident that the method of the invention attains a marked economic advantage over conventional processes.

The method of the invention may be employed with any type of reactor system, for example, employing fixed or iluidized catalyst beds, and with any type of catalyst. The method has particular advantage when used in connection with oxidation reactions carried out under pressure of from five to twenty-five atmospheres, which markedly increases the eiciency of the water scrubbing oxide recovery step, which is important in view of the relatively low concentration of ethylene oxide in the feed gases. As the scrubbing steps eliminate impurities found in small traces in the gaseous stream, a maximum eiiiciency of catalyst is maintained.

The oxidation of ethylene preferably may be carried out under operative reaction conditions of 220-350 C. temperature, and pressures of -25 atmospheres gauge, using ethylene in concentration of 1%-6%, with oxygen present in an amount from 5-18%. The operating conditions for the primary reactor, and the one or more secondary reactors, obviously will vary within these limits to attain the desired objectives of conversion, selectivity and yield prescribed as essential for maximum operating eiciency.

The method of the invention is used advantageously in connection with use of dilute feed gases as the source of ethylene, set forth in the co-pending application Serial Nos. 159,839 and 160,913, where the ,amount of feed gas removed in the purge, is greater than normal, which in turn would tend to decrease the overall efficiency of the method due to loss of ethylene.

While the invention has been described with reference to specific embodiments and examples shown herein, it is not to be regarded as limited thereby save as defined in the appended claims.

I claim:

1. A catalytic process for making olefin oxide by the oxidation of an olefin which comprises passing a gaseous reaction mixture containing oxygen and the olefin over a first silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the lower part of the range of about 23 to about 85%, removing olefin oxide from the resulting mixture, purging a portion of the remaining gaseous mixture and recycling the remaining portion over said catalyst, and passing the purged gaseous mixture over a second silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about l to 6 seconds to give a conversion in the upper part of the range of about 23 to about 85%,Y said conversion-being the ratio of the olefin reacted relative to the olefin fed, the yield of olefin oxide formed relative to the olefin reacted being higher at a relatively lower conversion, and recovering the resulting olefin oxide.

2. A catalytic process for making ethylene oxide by "the oxidation of ethylene which comprises passing a gaseous reaction mixture containing oxygen and ethylene over a first silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the lower part of the range of about 23 to about 85%, removing ethylene oxide from `the resulting mixture purging a portion of the remaining gaseous mixture and recycling the remaining portion over said catalyst, and passing the purged gaseous mixture over a second silver catalyst at a temperature in the range of about 220` to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the upper part of the range of about 23 to about 85%, said conversion being the ratio of the ethylene reacted relative to the ethylene fed, the yield of ethylene oxide formed relative to the ethylene reacted being higher at a relatively lowr conversion, and recovering the resulting ethylene 0x1 e.

3. A catalytic process for making olefin oxide vby the oxidation of an olefin which comprises passing a gaseous reaction mixture containing oxygen and the olefin over a first silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the lower part of the range of about 23 to about removing olefin oxide from the resulting mixture, purging a portion of the remaining gaseous mixture and recycling the remaining portion over said catalyst, adding oxygen-containing gas to the purged gaseous mixture and passing the resulting mixture over a second silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the upper part of the range of about 23 to about 85%, said conversion being the ratio of the olefin reacted relative to the olefin fed, the yield of olefin oxide formed relative to the olefin reacted being higher at a relatively lowr conversion, and recovering the resulting olefin ox1 e.

4. A catalytic process for making ethylene oxide by the oxidation of ethylene which comprises passing a gaseous reaction mixture containing oxygen and 1 to 6% ethylene over a first silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the lower part of the range of about 23 to about 85%, removing ethylene oxide from the resulting mixture, purging a portion of the remaining gaseous mixture and recycling the remaining portion over said catalyst, adding oxygen-containing gas to the purged gaseous mixture and passing the resulting mixture over a second silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in 'the range of about 1 to 6 seconds to give a conversion in the upper part of the range of about 23 to about 85%, said conversion being the ratio of the ethylene reacted relative to the ethylene fed, the yield of ethylene oxide formed relative to the ethylene reacted being higher at a relatively lower conversion, and recovering the resulting ethylene oxide.

5. A catalytic process for making ethylene oxide by the oxidation of ethylene which comprises passing a gaseous reaction mixture containing oxygen and 1 to 6% ethylene over a first silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about 1 to 6 seconds to give a conversion in the lower part of the range of about 23 to about 85 removing ethylene oxide from the resulting mixture, purging a portion of the remaining gaseous mixture and recycling the remaining portion over said catalyst, adding oxygen-containing gas to the purged gaseous mixture and passing the resulting mixture over a second silver catalyst at a temperature in the range of about 220 to about 350 C. and a contact time in the range of about l to 6 seconds to give a conversion in the upper part of the range of about 23 to about 85%, removing ethylene oxide from the gaseous mixture which leaves the second catalyst, purging a portion of the remaining gaseous mixture and recycling gegaan Aing higher at a relatively lowr conversion, 'and rrecovin ering the resulting ethyleneoxide.

6. A catalyticprocess forfnraking ethylene-.oxideby the v.oxidation 'of ethylene wheh comprises passing la vgaseous v'reaction mixture'containing oxygen :and l'-1 to v6% ethylene `over a rst lsilver catalystfat atemperature in `therange of'about l22010 yabout 350C. andra -eon- Vtacttme in the range .of about 'l to`6 A:seconds tocgive .a `conversion `inthe lowler .partof the range of :about `23 'to about f85%, "removing'ethylene oxide from the resulting mixture, 'purging a portion :of 'the Vremaining gaseous mixture `and recycling 'the fren-.raining portion over said catalyst, adding oxygen-.eontaining .'gas 'tto the purged gaseous mixture and passing the'resulting mix- :ture *over .a second 'silver-catalyst `at 1.a -temperature in the range of about 220 to about 350 C. and acontact ,time in the range of -aboutfl'fto 6zse`conds-to5'give ;,a-conversion inthe upper -prt-oftherange'ofabout 23 to about 85%, the second-catalytic ltreating 'step ,being carried out'at a higher 'temperature i'than fthe rst .catalytic treating step, lsaidconversion being 'the ratio of`the ethylene reacted-relative1to1theethylenefed, theyieldof ethyleneoxide'tormed relativefto'tbe ethylene reacted being vhigher aat '1a relativelylower conversion, and recovering the resulting ethylene oxide.

7. Aeatalytic process for-making-ethylene oxideby wtheoxidation of ethylene which -comprises passing .aI

.a gaseous reaction'mixture.containing oxygen and 'l to 16% ethylene over a vflrstisilver*catalyst'at altemperature in the range of abouti220 to about 350 C. and acon- --tact timein the range of-about 1"to'61-seconds` toV give a conversion in the `lower part 4of-*the' tangent-#about '23 :toabout .85% ,f 'removing' ethylene oxide'- 'from the' result- `ing mixture, purginga portion ofthe'remaininggaseous mixture and recycling 'the vremaining:pension-lover-said catalyst, adding oxygenlcorrtainingf-gas to-the purged gaseous mixture and passing the resulting mixture overna-'sec- .ond silver catalyst at. a temperature in the .range of about `220M toV aboutl 350 C.-and a-cont'aet timefin the' range of about 1 tol 6 seconds-to f give' .a conversion in- :the

upper part of -the rangeof'about'23to -about"f85%,

removingv the ethylene oxide from tthe gaseous mixture' resultingV from the secondcatalytic' treating'- step, purgv`ing a portion of the remaining-gaseous ymixtureI and` recycling the resulting remainder over the secondeatalyst, said conversion 'being the ratio ofytl`1eethylenel reacted ArelativeV to the ethylene fed, Athe yield-.ofethyleneoxide `formed relative Yto the ethylene reacted being higherfat -a relatively lower conversion, :and recovering v:the lresulting ethylene oxide.

8.- `A catalytic process for making-:ethylene .oxide ously passing .a gaseous reaction mixturefcontainingtoxy- =gen fand '1' to 6%4 ethylene `over xa Ir-st' silver catalyst at f a' temperaturein :the range offkabout- `220"to` .about :.350` Cfandza'contacttime -in the -range .ofvabo'utl l -to -6 seconds-:to giveaeconyersion -belowia'bout 50% and' in the lower part of the range Aof'about23'f-to-about "85%, removing .ethylenev oxide from the resulting-mixturefl purging' ati-'portionv of the 1 gaseous'lmixt-ure and-1 ^recyeling the remaining portion over saidcatalyst,-adding,

.oxygen-containingvgas Ito; the' purged*gaseousf'mixture' *andpassing the resulting" mixture overa-.second silver Vcatalystiatfa temperature in-the range offabout 220 -to -about 350 C. and a cont-act Vtime in .the range of about il" 'to '-6 secondsy to* give a* conversion l /inthe upper part -9.A catalytic process for making ethylene oxide by l-'the oxidation of ethylene which .comprises .continuously passing a gaseous reaction mixture .containing oxygen and 1 to 6% .ethylene .over a rst silver catalyst .at a temperature in the range of about 220 to .about 350 C. and a contact time in the range of about 1=to 6-sec- Aond-s to give a conversion in the lower part of the range ofabout 23 to about 50%, removing the ethylene oxide from the resulting mixture, purging a portion of -the gaseous mixture and recycling the remaining .portion oversaid catalyst, adding oxygen-containing gas to the purged vgaseous'rnixture and passing the resulting mixture over a second silver catalyst at a temperature in the range .of about.220.to-about..350 C.an'd acontact ltime in `.the range .of about `l `to '.6 `seconds to -give a conversionin .the .upperpart .oft'he vrangeof about 23 -toabout 50%, removing the ethylene oxide from the gaseous mixture resulting.from-the-second catalytic treatyrecovering the-resulting ethylene oxide.

l`0.-A catalytic-process -for-making'zethylene oxide-by the oxidation of ethylene which comprises passing a gaseous reaction mixture contalnmg oxygen and about 5% ethylene over Aa rst silver catalyst at atem-perature -ofabout 270 -C. for acontact time cnf-about l-second to f givea conversion inl the, lower part .of the range-,of about23 =.to yabout 85%,-removingethylene oxide from the resulting gaseous' mixture, .purging .a portion of the .gaseous-'mixture `and recycling the remaining portion over-saidcatalyst, add-ing loxygen-containing gas -to the purged gaseous mixture to forma gaseous mixture con- --tamingabout 3.5% ethylene and passingA the latter mixture over -asecond silver catalystata temperature of about 285 C. and afeontact .time .in ythe range of about 1 l to 3 seconds to( .give a conversion in the upperI part -of the range of about 23 *to` about 85% said lconversion :being the ratio of the ethylene reaeted'relative to'the ethylene fed, theyield offethylene oxide'fformed rela- --tive -to the ethylene reacted :being higher lat..a'relatively `lower conversion, and recoveringthe'resulting ethylene oxide.

l-l. A lcatalytic process' ffor making;ethylenewoxideby the oxidation of ethylene-which'comprises passing af gaseous reaction mixture'containing. oxygenandfabout 5% ethylene 'over aiirst silvercatalyst at aiftemperatureof labout 270 to 280 C. for: a'vcontact time of about 3.5 lseconds to give a Iconversion* in the'lower part of the rrange-of about 23 .to':about85%, :removing ethylene -foxide from the Vresultinggaseouslmixturq purging a portionof the gaseous-mixture and 'reeyclinglthe -remaining portion over. .said catalyst, Vadding oxygen-containing-'gas `to theHpurged gaseous mixtureto form a gaseous-'mixture containing about 3.5 ethylene and passing the -lat- `-termixture over a ysecond silver catalyst at a temper- 60 ature of about 275 to- 285\2C.:and amcontactitimelin the range of about 5 =to 6*'secondslto give' a`1convers'ion=in 'the upper pa'rt of -Ithe :rang'ef'about23 to1'aboutf185%, the second catalytic treating lstepibeing rcarried fout'at-a -higher `temperaturefthan thev rstcatalytic treating step,

said 'conversion being -the iratio4 .of :the ethylene .reacted relative to the ethylene fied; the yieldjofethiylene oxide i formed relative to ithe'- ethylene reaetedbeingihigheriat a relativelytlower conversiomand recoveringlthe'fresulting ethylene oxide.

References Cited infthertilerof. this patent UNITED STATES' PATENTS Number Nanne f Date 2,245,183 l.Christ f June ll0, 1941 2,393,240 `Dreyfus Jan. 22, :1946 2,437,930 Bergsteinsson Mar.` 16,' :19.48 2,458,266 Heider Jan-4,` 19.49

FOREIGN PATENTS Number Country ...Date

472,629 Great Britain :1937 531,256 Great Brita-in ..1941 560,770 Great Britain 1119.42 573,575 -Great vBritain Now/.27,1945 

1. A CATALYTIC PROCESS FOR MAKING OLEFIN OXIDE BY THE OXIDATION OF AN OLEFIN WHICH COMPRISES PASSING A GASEOUS FIRST SILVER CATALYST AT A TEMPERATURE IN THE RANGE OF ABOUT REACTION MIXTURE CONTAINING OXYGEN AND THE OLEFIN OVER A 220 TO ABOUT 350* C. AND A CONTACT TIME IN THE RANGE OF ABOUT 1 TO 6 SECONDS TO GICA A CONVERSION IN THE LOWER PART OF THE RANGE OF ABOUT 23 TO ABOUT 85%, REMOVING OLEFIN OXIDE FROM THE RESULTING MIXTURE, PURGNG A PORTION OF THE REMAINING GASEOUS MIXTURE, PURGING A PORTION MAINING PORTION OVER SAID CATALYST, AND PASSING THE PURGED GASEOUS MIXTURE OVER A SECOND SILVER CATALYST AT A TEMPERATURE IN THE RANGE OF ABOUT 220 TO ABOUT 350* C. AND A CONTACT TIME IN THE RANGE OF ABOUT 1 TO 6 SECONDS TO GIVE A CONVERSION IN THE UPPER PART OF THE RANGE OF ABOUT 23 TO ABOUT 85%, SAID CONVERSION BEING THE RATION OF THE OLEFIN REACTED RELATICE TO THE OLEFIN FED, THE YIELD OF OLEFIN OXIDE FORMED RELATIVE TO THE OLEFIN REACTED BEING HIGHER AT A RELATIVELY LOWER CONVERSION, AND RECOVERING THE RESULTING OLEFIN OXIDE. 